KR20110048525A - Carbon Nanotube-Reinforced Nanocomposites - Google Patents
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Abstract
탄소 나노튜브 (CNT)는 너무 길어서 이러한 탄소 나노튜브가 프리프레그 제조 공정 동안에 탄소 섬유 사이로 관통될 수 없으며, 이는 탄소 섬유에 의해 새어나오지 않도록 하기 위해 단축된다. 이는 순수한 에폭시와 비교하여 기계적 성질 (굴곡 강도 및 굴곡 탄성율)을 상당히 개선시킨다.Carbon nanotubes (CNTs) are so long that such carbon nanotubes cannot penetrate between carbon fibers during the prepreg fabrication process, which is shortened to prevent leakage by the carbon fibers. This significantly improves the mechanical properties (flexural strength and flexural modulus) compared to pure epoxy.
Description
본 출원은 미국가출원번호 제60/819,319호 및 제60/810,394호를 우선권으로 주장하는 미국특허출원번호 제11/757,272호의 일부계속출원으로서, 이러한 문헌 모두는 본원에 참고문헌으로 포함된다. 본 출원은 미국가출원번호 제60/788,234호 및 제60/810,394호를 우선권으로 주장하는 미국특허출원번호 제11/693,454호의 일부계속출원으로서, 이러한 문헌 모두는 본원에 참고문헌으로 포함된다. 본 출원은 미국가출원번호 제60/789,300호 및 제60/810,394호를 우선권으로 주장하는 미국특허출원번호 제11/695,877호의 일부계속출원으로서, 이러한 문헌 모두는 본원에 참고문헌으로 포함된다.This application is partly filed in US Patent Application No. 11 / 757,272, which claims priority to US Provisional Application Nos. 60 / 819,319 and 60 / 810,394, all of which are incorporated herein by reference. This application is partly filed in US patent application Ser. No. 11 / 693,454, which claims priority to US Provisional Application Nos. 60 / 788,234 and 60 / 810,394, all of which are incorporated herein by reference. This application is partly filed in US Patent Application No. 11 / 695,877, which claims priority to US Provisional Application Nos. 60 / 789,300 and 60 / 810,394, all of which are incorporated herein by reference.
1991년 첫 관찰 이후에, 탄소 나노튜브 (CNT)는 상당한 연구의 중심이 되어 왔다[S. Iijima, "Helical microtubules fo graphitic carbon", Nature 354, 56 (1991)]. 많은 연구가들이 이러한 새로운 형태의 탄소의 주목할만한 물리적 및 기계적 특성을 보고하였다. CNT는 전형적으로 단일벽 CNT (SWNT)에 있어서 0.5-1.5nm, 이중벽 CNT (DWNT)에 있어서는 1-3nm, 및 다중벽 CNT (MWNT)에 있어서는 5 내지 100nm의 직경을 갖는다. 독특한 전자 특성 및 다이아몬드보다 더 높은 열전도성, 내지 강성, 강도 및 탄성이 통용되는 재료보다 높은 기계적 특성으로부터, CNT는 기본적인 새로운 재료 시스템의 개발에 굉장한 기회를 제공한다. 특히, 저밀도 (1-2.0g/cm3)와 함께 CNT의 특별한 기계적 특성 (E > 1.0 TPa 및 50 GPa의 인장 강도)으로 인해 CNT-보강된 복합체 재료의 개발이 관심을 끌었다[Eric W. Wong, Paul E. Sheehan, Charles M.Lieber, "Nanobeam Mechnics: Elasticity, Strength, and Toughness of Nanorods and Nonotubes", Science 277, 1971 (1997)]. CNT는 지구상에서 알려진 가장 강한 재료이다. MWNT와 비교할 경우, SWNT 및 DWNT는 이들의 높은 표면적 및 높은 종횡비로 인해 복합체용 보강 재료로서 더욱 유망하다. 표 1은 SWNT, DWNT 및 MWNT의 표면적 및 종횡비를 나타낸 것이다.Since its first observation in 1991, carbon nanotubes (CNTs) have been the center of considerable research [S. Iijima, "Helical microtubules fo graphitic carbon", Nature 354, 56 (1991). Many researchers have reported the remarkable physical and mechanical properties of this new type of carbon. CNTs typically have diameters of 0.5-1.5 nm for single wall CNTs (SWNTs), 1-3 nm for double wall CNTs (DWNTs) and 5 to 100 nm for multiwall CNTs (MWNTs). From the unique electronic properties and higher mechanical properties of materials with higher thermal conductivity, to stiffness, strength and elasticity than diamond, CNT offers great opportunities for the development of basic new material systems. In particular, the development of CNT-reinforced composite materials attracted interest due to the low mechanical density (1-2.0 g / cm 3 ) and the special mechanical properties of CNTs (tensile strength of E> 1.0 TPa and 50 GPa) [Eric W. Wong Paul E. Sheehan, Charles M. Lieber, "Nanobeam Mechnics: Elasticity, Strength, and Toughness of Nanorods and Nonotubes", Science 277, 1971 (1997). CNT is the strongest material known on earth. Compared with MWNTs, SWNTs and DWNTs are more promising as reinforcing materials for composites because of their high surface area and high aspect ratio. Table 1 shows the surface area and aspect ratio of SWNTs, DWNTs and MWNTs.
표 1TABLE 1
문제는 CNT가 성장될 때 대개 상당히 길다(수 마이크론 내지 100 ㎛ 이상)는 것인데, 이는 가장 가까운 섬유들 사이의 거리가 너무 짧기 때문에 CNT가 섬유 보강된 플라스틱 (FRP)에서 매트릭스에 관통되기 어렵게 만든다. 예를 들어, 일방향 탄소 섬유 또는 섬유 보강된 에폭시 복합체의 경우에, 탄소 섬유의 함량은, 가장 가까운 탄소 섬유들 사이의 갭이 대략 1 마이크론 (탄소 섬유가 7-8 ㎛의 직경을 가지고 대략 1.75 - 1.80 g/㎤의 밀도를 가지며, 에폭시 매트릭스가 1.2 g/㎤의 밀도를 갖는다고 가정)이도록 대략 60 부피%이다. 이는 복합체를 제조하기 위해 사용되는 유리 섬유 및 다른 타입의 섬유에 대해서도 마찬가지다. CNT는 강도 및 모듈러스(modulus)와 같은 기계적 성질을 개선시키기 위해 폴리머 수지를 보강할 수 있지만, 이러한 것들은 FRP 제조 동안에 섬유에 의해 새어나오기(filtered out) 때문에 FRP를 보강할 수 없다.The problem is that when CNTs are grown, they are usually quite long (a few microns to 100 μm or more), which makes CNTs difficult to penetrate the matrix in fiber reinforced plastics (FRP) because the distance between the nearest fibers is too short. For example, in the case of unidirectional carbon fibers or fiber reinforced epoxy composites, the content of carbon fibers is such that the gap between the nearest carbon fibers is approximately 1 micron (carbon fibers have a diameter of 7-8 μm and approximately 1.75 − Approximately 80% by volume), with a density of 1.80 g / cm 3 and assuming that the epoxy matrix has a density of 1.2 g / cm 3. The same is true for the glass fibers and other types of fibers used to make the composites. CNTs can reinforce polymer resins to improve mechanical properties such as strength and modulus, but they cannot reinforce FRP because they are filtered out by fibers during FRP manufacture.
도 1은 본 발명의 일 구체예에 따른 나노복합체를 제조하는 방법을 도시한 것이다.
도 2는 MWNT의 SEM 디지털 이미지를 도시한 것이다.
도 3a 내지 도 3c는 MWNT-보강된 에폭시, DWNT-보강된 에폭시, 및 SWNT-보강된 에폭시 각각의 파괴면(fracture surface)의 SEM 디지털 이미지를 도시한 것이다.
도 4a는 DWNT-보강된 CFRP의 파괴면의 SEM 디지털 이미지를 도시한 것으로서, 탄소 섬유 사이에 DWNT가 관통되지 않은 것으로 나타나 있다.
도 4b는 DWNT-보강된 CFRP의 파괴면의 SEM 디지털 이미지를 도시한 것으로서, 프리프레그의 단부층(end layer) 밖으로 새어나옴을 나타내고 있다.
도 5a 내지 도 5c는 단축된(shortened) MWNT, DWNT, 및 SWNT 각각의 SEM 디지털 이미지를 도시한 것이다.
도 6a 내지 도 6c는 MWNT-보강된 CFRP, DWNT-보강된 CFRP, 및 SWNT-보강된 CFRP 각각의 파괴면의 SEM 디지털 이미지를 도시한 것이다.1 illustrates a method of manufacturing a nanocomposite according to an embodiment of the present invention.
2 shows an SEM digital image of MWNTs.
3A-3C show SEM digital images of the fracture surfaces of each of the MWNT-reinforced epoxy, DWNT-reinforced epoxy, and SWNT-reinforced epoxy.
4A shows a SEM digital image of the fracture surface of DWNT-reinforced CFRP, showing no DWNT penetration between the carbon fibers.
4B shows a SEM digital image of the fracture surface of the DWNT-reinforced CFRP, showing leaking out of the end layer of the prepreg.
5A-5C show SEM digital images of shortened MWNTs, DWNTs, and SWNTs, respectively.
6A-6C show SEM digital images of fracture surfaces of MWNT-reinforced CFRP, DWNT-reinforced CFRP, and SWNT-reinforced CFRP, respectively.
2 ㎛ 정도로 짧거나 이보다 더욱 짧은 CNT는 섬유 사이로 관통될 수 있으며, 이에 따라 FRP의 기계적 성질을 현저히 개선시킨다.CNTs as short as or shorter than 2 μm can penetrate between fibers, thereby significantly improving the mechanical properties of the FRP.
본 발명의 일 구체예에서, 본 구체예의 상세한 예는 본 발명을 보다 잘 예시하기 위한 노력의 일환으로 제공된다.In one embodiment of the invention, detailed examples of this embodiment are provided in an effort to better illustrate the invention.
에폭시, Epoxy, SWNTSWNT , , DWNTDWNT , , MWNTMWNT , 및 경화제, And hardeners
에폭시 수지 (비스페놀-A)는 아리사와 인크(Arisawa Inc., Japan)로부터 입수되었다. 경화제 (디시안디아미드)는 동일한 회사로부터 입수되었으며, 이는 에폭시 나노 복합체를 경화시키는데 사용되었다. SWNT, DWNT 및 MWNT는 나노실 인크(Nanocyl, Inc., Belgium)로부터 입수되었다. CNT는 90% 초과의 탄소 함량으로 정제될 수 있다. 그러나, 본래의 CNT 또는 카르복실 및 아미노-작용기와 같은 작용기에 의해 작용화된 CNT가 또한 사용될 수 있다. CNT의 길이는 대략 5 내지 20 ㎛일 수 있다. 도 2는 MWNT의 SEM의 디지털 이미지를 도시한 것이다. 에폭시를 제외하고, 폴리이미드, 페놀계 수지, 시아네이트 에스테르, 및 비스말레이미드와 같은 다른 열경화성 물질 또는 나일론과 같은 열가소성 물질이 또한 사용될 수 있다.Epoxy resin (bisphenol-A) was obtained from Arisawa Inc., Japan. Curing agent (dicyandiamide) was obtained from the same company, which was used to cure epoxy nanocomposites. SWNTs, DWNTs and MWNTs were obtained from Nanocyl, Inc., Belgium. CNTs can be purified to a carbon content of greater than 90%. However, native CNTs or CNTs functionalized by functional groups such as carboxyl and amino-functional groups can also be used. The length of the CNTs may be approximately 5-20 μm. 2 shows a digital image of the SEM of the MWNT. Except for epoxy, other thermosetting materials such as polyimide, phenolic resins, cyanate esters, and bismaleimide or thermoplastics such as nylon can also be used.
도 1은 본 발명의 일 구체예에 따른 에폭시/CNT 나노 복합체를 제조하기 위한 공정 흐름의 개략적인 다이아그램을 도시한 것이다. 모든 성분들은 수분을 제거하기 위하여 70℃의 진공 오븐에서 16 시간 동안 건조될 수 있다. 수지 각각에 대해 CNT의 적재량은 1.0 중량%일 수 있다. CNT는 아세톤 중에 배치되고(101), 단계(102)에서 미세-유체 기기에 의해 분산된다 (Microfluidics Co.로부터 상업적으로 입수가능, 모델 번호. Y110). 미세-유체 기기는 정밀하게 규정된 마이크로-크기의 채널에서 초고속으로 충돌하는 고압 스트림을 이용한다. 이의 전단력과 충격력의 조합된 힘은 균일한 분산액을 생성시키기 위해 생성물 상에서 작용한다. 이후에 CNT/아세톤은 아세톤 용매 중에 CNT가 잘 분산된 겔로서 형성된다(103). 그러나, 초음파 공정 또는 고전단 혼합 공정과 같은 다른 방법들이 또한 사용될 수 있다. 계면활성제가 또한 용액 중에 CNT를 분산시키기 위하여 사용될 수 있다. 이후에 에폭시는 단계(104)에서 CNT/아세톤에 첨가되어 에폭시/CNT/아세톤 용액을 생성시키고(105), 이는 70℃의 배스에서 1 시간 동안 초음파 공정으로 처리되어 에폭시/CNT/아세톤 현탁액을 생성시킨다(107). CNT는 단계(108)에서 70℃에서 30분 동안 1,400 회/분의 속도로 교반기 혼합 공정을 이용하여 에폭시 중에 추가로 분산되어, 에폭시/CNT/아세톤 겔을 생성시킨다(109). 경화제는 이후에 단계(110)에서 에폭시/CNT/아세톤 겔(109)에 4.5 중량%의 비율로 첨가된 후에 70℃에서 1 시간 동안 교반한다. 얻어진 겔(111)은 이후에 단계(112)에서 70℃의 진공 오븐에서 48 시간 동안 탈기될 수 있다. 이러한 물질(113)은 이후에 160℃에서 2 시간 동안 경화될 수 있다. 물질(113)을 시험하기 위하여, 이는 이후에 시편의 기계적 성질(굴곡 강도 및 굴곡 탄성율)이 연마 공정(115) 후에 특징화되도록 테플론 주형에 부어질 수 있다.1 shows a schematic diagram of a process flow for producing an epoxy / CNT nanocomposite according to one embodiment of the invention. All components can be dried for 16 hours in a 70 ° C. vacuum oven to remove moisture. The loading of CNTs for each of the resins can be 1.0 weight percent. The CNTs are placed in acetone (101) and dispersed by micro-fluidic device in step 102 (commercially available from Microfluidics Co., Model No. Y110). Micro-fluidic devices utilize high pressure streams that collide at very high speeds in precisely defined micro-sized channels. Its combined force of shear and impact forces acts on the product to produce a uniform dispersion. CNT / acetone is then formed as a gel in which CNTs are well dispersed in acetone solvent (103). However, other methods may also be used, such as an ultrasonic process or a high shear mixing process. Surfactants can also be used to disperse the CNTs in solution. The epoxy is then added to the CNT / acetone in step 104 to produce an epoxy / CNT / acetone solution (105), which is subjected to an ultrasonic process for 1 hour in a bath at 70 ° C. to produce an epoxy / CNT / acetone suspension. (107). The CNTs are further dispersed in epoxy using a stirrer mixing process at a rate of 1,400 cycles / minute for 30 minutes at 70 ° C. in
70℃에서 48 시간 동안 탈기된 후 상기 수지 (에폭시/CNT/경화제)는 또한 핫-멜트 공정(hot-melt process)을 이용하여 FRP를 제조하기 위해 사용될 수 있다. 탄소 섬유 (Toray Industries, Inc.로부터 입수가능, 모델번호 T700-12k)는 프리프레그(prepreg) 제조를 위해 사용될 수 있다. "프리프레그" (또는 "pre-preg")는 "사전-함침된" 복합체 섬유에 대한 당해 분야에서 공지된 용어이다. 이러한 것들은 직물(weave) 형태를 가지거나 일방향(unidirectional)일 수 있다. 이러한 것들은 이러한 것들을 함께 결합시키고 제조 동안에 다른 성분들에 결합시키기 위해 사용되는 일정한 양의 매트릭스 물질을 함유한다. 프리프레그는 활성화가 가장 일반적으로 열에 의해 진행되기 때문에 냉각된 구역에 저장될 수 있다. 이에 따라, 프리프레그의 복합체 구조 성장(buildup)은 경화를 위한 오븐 또는 오토클래브를 대부분 요구할 것이다.After degassing at 70 ° C. for 48 hours, the resin (epoxy / CNT / curing agent) can also be used to prepare FRP using a hot-melt process. Carbon fibers (available from Toray Industries, Inc., model number T700-12k) can be used for prepreg production. "Prepreg" (or "pre-preg") is a term known in the art for "pre-impregnated" composite fibers. These may have a weave form or may be unidirectional. These contain a certain amount of matrix material used to bond these together and to other components during manufacture. The prepreg can be stored in a cooled zone because activation is most commonly carried out by heat. Accordingly, composite structure buildup of the prepreg will most likely require an oven or autoclave for curing.
CNT-보강된 에폭시 수지는 먼저 이형지 상에 코팅된다. 프리프레그는 이후에 일방향 탄소 섬유를 CNT-보강된 에폭시 수지 박막으로 함침시킴으로써 얻어진다. 탄소 섬유의 부피는 60%로 조절되었다. 프리프레그는 180 g/㎡의 단위 면적당 중량(area weight)을 갖는다.The CNT-reinforced epoxy resin is first coated on a release paper. The prepreg is then obtained by impregnating unidirectional carbon fibers with a thin film of CNT-reinforced epoxy resin. The volume of carbon fiber was adjusted to 60%. The prepreg has an area weight of 180 g / m 2.
나노 복합체의 기계적 성질Mechanical Properties of Nanocomposites
표 2는 일방향 탄소 섬유의 보강과 함께 CNT-보강된 에폭시의 기계적 성질(굴곡 강도 및 굴곡 탄성율)을 나타낸 것이다. 이러한 표에서는 수지 형태에서, 순수한 에폭시와 비교하여 기계적 성질의 상당한 개선을 나타내고 있다 (굴곡 강도는 30% 초과 개선, 및 굴곡 탄성율은 적어도 10% 개선). 그러나, 탄소 섬유 보강된 폴리머 (CFRP) 형태에서, 둘 모두의 성질들은 순수한 에폭시 CFRP와 비교하여 CNT-보강된 CFRP의 경우에 개선되지 않았다.Table 2 shows the mechanical properties (flexural strength and flexural modulus) of CNT-reinforced epoxy with reinforcement of unidirectional carbon fibers. This table shows, in the resin form, a significant improvement in mechanical properties compared to pure epoxy (flexural strength is more than 30% improvement, and flexural modulus is at least 10% improvement). However, in the form of carbon fiber reinforced polymer (CFRP), the properties of both did not improve in the case of CNT-reinforced CFRP compared to pure epoxy CFRP.
표 2TABLE 2
주사전자현미경 (SEM)은 수지 및 CFRP 샘플 모두에서 CNT의 분산을 체크하기 위하여 사용될 수 있다. 수지 형태에서, 모든 CNT-보강된 에폭시 샘플은 CNT의 매우 양호한 분산을 나타내었다 (도 3a 내지 도 3c 참조). 그러나, CNT는 일방향 탄소 섬유에 의해 프리프레그의 단부층으로 새어나왔다(DWNT-보강된 에폭시 CFRP에 대한 도 4a 및 도 4b 참조). 이는 가장 가까운 탄소 섬유에 대한 갭(gap)이 단지 대략 1 ㎛인 바 CNT가 너무 길어서 이러한 것들이 탄소 섬유 사이로 관통될 수 없기 때문이다. 이는 수지에서의 CNT의 보강이 CFRP로 이동하지 않는 이유이다.Scanning electron microscopy (SEM) can be used to check the dispersion of CNTs in both resin and CFRP samples. In the resin form, all CNT-reinforced epoxy samples showed very good dispersion of CNTs (see FIGS. 3A-3C). However, CNTs were leaked into the end layer of the prepreg by unidirectional carbon fibers (see FIGS. 4A and 4B for DWNT-reinforced epoxy CFRP). This is because the gap for the nearest carbon fiber is only approximately 1 μm, so the CNTs are too long such that they cannot penetrate between the carbon fibers. This is why the reinforcement of CNTs in the resin does not migrate to CFRP.
CNTCNT 의 단축, 및 에폭시 수지 및 Shortening, and epoxy resin and CFRPCFRP 의 보강Reinforcement
CNT가 너무 길어서 이러한 것들이 프리프레그 제조 공정 동안에 탄소 섬유 사이로 관통될 수 없기 때문에, CNT는 탄소 섬유에 의해 새어나오지 않도록 하기 위하여 단축되어야 한다. MWNT, DWNT, 및 SWNT는 진한 산 혼합물 (HNO3:H2SO4=3:1)과 혼합되고 120℃에서 4 시간 동안 교반될 수 있다. CNT는 여과지 (산을 여과하기 위한 2 마이크론 개구를 갖는 폴리카르보네이트 여과지)를 이용하여 여과된다. CNT는 이후에 이온수로 4 내지 5회 세척되고 진공 중 50℃ 이상에서 12 시간 동안 건조시켰다. 도 5a 내지 도 5c에서는 2 ㎛ 미만의 길이로 단축화된 MWNT, DWNT 및 SWNT 각각의 SEM 이미지를 나타낸 것이다.Since the CNTs are so long that these cannot be penetrated between the carbon fibers during the prepreg manufacturing process, the CNTs must be shortened to prevent leakage by the carbon fibers. MWNT, DWNT, and SWNT can be mixed with a concentrated acid mixture (HNO 3 : H 2 SO 4 = 3: 1) and stirred at 120 ° C. for 4 hours. CNTs are filtered using filter paper (polycarbonate filter paper with a 2 micron opening for filtering acid). The CNTs were then washed 4 to 5 times with ionized water and dried at 50 ° C. or higher in vacuo for 12 hours. 5A-5C show SEM images of MWNTs, DWNTs, and SWNTs each shortened to a length of less than 2 μm.
표 3은 일방향 탄소 섬유의 보강과 함께, 단축화된 CNT-보강된 에폭시의 기계적 성질(굴곡 강도 및 굴곡 탄성율)을 나타낸 것이다. 표 3에서는 수지 형태에서 순수한 에폭시와 비교하여 기계적 성질의 큰 개선을 나타내고 있으며(굴곡 강도는 30% 이상의 개선, 및 굴곡 탄성율은 적어도 10% 개선), 이는 상기 언급된 긴 CNT-보강된 에폭시 수지와 유사하다. CFRP 형태에서, 둘 모두의 성질은 순수한 에폭시 CFRP와 비교하여 개선되었다. 예를 들어, SWNT-보강된 CFRP의 굴곡 강도는 순수한 에폭시 CFRP와 비교하여 17% 개선되었다.Table 3 shows the mechanical properties (flexural strength and flexural modulus) of shortened CNT-reinforced epoxy with reinforcement of unidirectional carbon fibers. Table 3 shows a significant improvement in the mechanical properties compared to pure epoxy in the resin form (an improvement in flexural strength of at least 30% and an improvement in flexural modulus of at least 10%), which are in line with the above mentioned long CNT-reinforced epoxy resins. similar. In the CFRP form, the properties of both were improved compared to pure epoxy CFRP. For example, the flexural strength of SWNT-reinforced CFRP was improved by 17% compared to pure epoxy CFRP.
표 3TABLE 3
주사전자현미경 (SEM)은 CFRP 샘플에서 CNT의 분산을 체크하기 위해 사용될 수 있다. 도 6a 내지 도 6c에 도시된 바와 같이, 단축화된 MWNT, DWNT, 및 SWNT는 탄소 섬유 사이로 관통되고 잘 분산된다.Scanning electron microscopy (SEM) can be used to check the dispersion of CNTs in CFRP samples. As shown in FIGS. 6A-6C, shortened MWNTs, DWNTs, and SWNTs are penetrated between carbon fibers and well dispersed.
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2008
- 2008-07-25 US US12/180,359 patent/US8283403B2/en not_active Expired - Fee Related
- 2008-09-30 KR KR1020117004061A patent/KR20110048525A/en not_active Application Discontinuation
- 2008-09-30 WO PCT/US2008/078306 patent/WO2010011234A1/en active Application Filing
- 2008-09-30 CN CN2008801309960A patent/CN102137754A/en active Pending
- 2008-09-30 JP JP2011520015A patent/JP5568553B2/en not_active Expired - Fee Related
- 2008-09-30 TW TW097137566A patent/TW201005012A/en unknown
- 2008-09-30 EP EP08876637A patent/EP2315661A4/en not_active Withdrawn
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- 2012-10-08 US US13/647,017 patent/US20130059947A1/en not_active Abandoned
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JP5568553B2 (en) | 2014-08-06 |
EP2315661A4 (en) | 2013-01-09 |
EP2315661A1 (en) | 2011-05-04 |
US8283403B2 (en) | 2012-10-09 |
TW201005012A (en) | 2010-02-01 |
WO2010011234A1 (en) | 2010-01-28 |
US20130059947A1 (en) | 2013-03-07 |
US20090035570A1 (en) | 2009-02-05 |
JP2011529113A (en) | 2011-12-01 |
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